ANTIBACTERIAL POLYMER COATING COMPOSITION AND ANTIBACTERIAL POLYMER FILM

Abstract

The present disclosure relates to an antibacterial coating composition including a (meth)acrylate-based monomer or oligomer containing an alkylene oxide having 1 to 10 carbon atoms; a compound represented by the following Chemical Formula 1; and a photoinitiator, an antibacterial polymer film including a cured product of the antibacterial polymer coating composition, and an antibacterial polymer film including a polymer resin containing a (meth)acrylate-based repeating unit having an introduced alkylene oxide functional group having 1 to 10 carbon atoms; and a compound represented by the following Chemical Formula 1 dispersed in the polymer resin, wherein antibacterial activity measured according to JIS R 1702 (KS L ISO 27447; 2011) is 99% or more:

##STR00001## in Chemical Formula 1, at least one of R is

##STR00002##

and the rest are hydrogen, R.sub.1 is hydrogen, C1 to C5 alkyl, or C1 to C5 alkoxy, k is an integer of 1 to 5, and n is an integer of 1 to 20.

Claims

1. An antibacterial polymer coating composition comprising a (meth)acrylate-based monomer or oligomer containing an alkylene oxide having 1 to 10 carbon atoms; a compound represented by the following Chemical Formula 1; and a photoinitiator: ##STR00014## in the Chemical Formula 1, at least one R is ##STR00015## and each of the remaining R's is hydrogen, R.sub.1 is hydrogen, C1 to C5 alkyl, or C1 to C5 alkoxy, k is an integer of 1 to 5, and n is an integer of 1 to 20.

2. The antibacterial polymer coating composition of claim 1, wherein in the Chemical Formula 1, all of the R's are ##STR00016##

3. The antibacterial polymer coating composition of claim 1, wherein n is an integer of 2 to 10.

4. The antibacterial polymer coating composition of claim 1, wherein R.sub.1 is hydrogen, methyl, or methoxy.

5. The antibacterial polymer coating composition of claim 1, wherein k is 2 or 3.

6. The antibacterial polymer coating composition of claim 1, wherein the (meth)acrylate-based monomer or oligomer is a mono(meth)acrylate-based monomer or oligomer containing an alkylene oxide having 1 to 10 carbon atoms; or a di(meth)acrylate-based monomer or oligomer containing an alkylene oxide having 1 to 10 carbon atoms.

7. The antibacterial polymer coating composition of claim 6, wherein the di(meth)acrylate-based monomer or oligomer containing an alkylene oxide having 1 to 10 carbon atoms is represented by the following Chemical Formula 2: ##STR00017## in the Chemical Formula 2, R.sub.11 and R.sub.16 are each independently hydrogen or C1 to C3 alkyl; R.sub.12 to R.sub.15 are the same as or different from each other, and are each independently C1 to C4 alkylene; and n1 to n4 represent an addition mole number of alkylene oxide repeating units and are the same as or different from each other, and are each independently an integer of 0 to 13, and n1+n2+n3+n4 is 1 to 13, in which random or block phases are formed by a mixed composition of one or more of the alkylene oxides.

8. The antibacterial polymer coating composition of claim 1, wherein the (meth)acrylate-based monomer or oligomer has a weight average molecular weight of 500 g/mol to 10000 g/mol.

9. The antibacterial polymer coating composition of claim 1, wherein 0.01 to 5 parts by weight of the compound represented by the Chemical Formula 1 is included based on 100 parts by weight of the (meth)acrylate-based monomer or oligomer.

10. The antibacterial polymer coating composition of claim 1, further comprising an organic solvent, a surfactant, or a mixture thereof.

11. The antibacterial polymer coating composition of claim 1, further comprising a monomer or oligomer containing (meth)acrylate different from the (meth)acrylate-based monomer or oligomer containing an alkylene oxide having 1 to 10 carbon atoms; or a monomer or oligomer containing a vinyl group.

12. An antibacterial polymer film, comprising a cured product of the antibacterial polymer coating composition of claim 1.

13. An antibacterial polymer film, comprising a substrate layer including a polymer resin containing a (meth)acrylate-based repeating unit having an introduced alkylene oxide functional group having 1 to 10 carbon atoms, and a photosensitizer dispersed in the substrate layer, wherein the photosensitizer includes a compound represented by the following Chemical Formula 1, wherein an antibacterial activity as measured according to JIS R 1702 (KS L ISO 27447; 2011) is at least 99%, ##STR00018## in the Chemical Formula 1, at least one R is ##STR00019## and each of the remaining R's is hydrogen, R.sub.1 is hydrogen, C1 to C5 alkyl, or C1 to C5 alkoxy, k is an integer of 1 to 5, and n is an integer of 1 to 20.

14. (canceled)

15. (canceled)

16. An electronic product comprising the antibacterial polymer film of claim 12.

17. The electronic product of claim 13, wherein the electronic product is a humidifier, a refrigerator, an air washer, or an aquarium.

18. An electronic product comprising the antibacterial polymer film of claim 13.

19. The electronic product of claim 18, wherein the electronic product is a humidifier, a refrigerator, an air washer, or an aquarium.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0077] FIG. 1 shows the result of NMR analysis of the product of Preparation Example 1.

[0078] FIG. 2 schematically shows a method for measuring the antibacterial activity of the polymer films of Examples and Comparative Examples according to JIS R 1702 (KS ISO 27447) in Experimental Example 1.

[0079] FIG. 3 shows the result of the antibacterial activity of the polymer films of Examples and Comparative Examples according to Experimental Example 1.

[0080] Embodiments of the present invention are described in more detail by way of the examples provided below. However, the following examples are given for illustrative purposes only, and the scope of the present invention is not intended to be limited to or by these examples.

Preparation Example: Preparation of Raw Material

Preparation Example 1: Preparation of (Meth)Acrylate-Based Oligomer Containing an Alkylene Oxide Having 1 to 10 Carbon Atoms

[0081] A (meth)acrylate-based oligomer containing an alkylene oxide having 1 to 10 carbon atoms was prepared according to the following Reaction Scheme.

[0082] Specifically, 14 g of PEG400 (polyethylene glycol 400) was dispersed in a mixed solution of 5 g of potassium carbonate (K2003) and 50 g of dimethyl sulfoxide, and then mixed for 30 minutes (0° C., N.sub.2 purging conditions).

[0083] Then, 10 g of 2-chloroethyl acrylate (M.W. of 134.56 g/mol) was added thereto and reacted for 3 hours. The reaction product was obtained through a column, and it was confirmed whether an alkylene oxide (meth)acrylate of the following Reaction Scheme 1 was produced from the result of NMR analysis (FIG. 1) and GC-MS analysis (weight average molecular weight: 610.69).

##STR00011##

Preparation Example 2: Preparation of Photosensitizer (Compound Represented by Chemical Formula 1)

[0084] TCPP (4,4′,4″,4′″-(porphrin-5,10,15,20-tetrayl)tetrakis(benzoic acid); 1 eq) purchased from Sigma-Aldrich was dissolved in DMF, and then poly(ethylene glycol) monomethyl ether (weight average molecular weight: 400; 10 eq) was added thereto through a syringe at 0° C. After 10 minutes at 0° C., DMAP (4-(dimethylamino)pyridine; 1 eq) was added thereto. After 30 minutes at 0° C., EDC.HCl (N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride; 10 eq) was added thereto. When the reaction was completed, DMF used as a solvent was dried to remove, and extracted with water. The extract was purified by column chromatography after removal of water using magnesium sulfate, thereby preparing a compound having the following structure among the compounds represented by the Chemical Formula 1.

[0085] In the above process, a weight average molecular weight of poly(ethylene glycol) monomethyl ether was adjusted to control n of the compound having the following structure. Herein, the smaller the weight average molecular weight of the poly(ethylene glycol) monomethyl ether, the smaller n the compound may have.

[0086] Accordingly, a compound having n of 2 to 4, a compound having n of 5 to 7, and a compound having n of 8 to 10 were obtained, and used in Example 1 (n=2˜4), Example 2 (n=5˜7), and Example 3 and Comparative Example 2 (n=8˜10), respectively.

[0087] .sup.1H NMR (500 MHz, CDCl.sub.3, ppm): 8.82 (s, 8H), 8.47-8.46 (d, 8H), 8.30-8.29 (d, 8H), 4.68-4.66 (t, 8H), 4.00-3.97 (t, 8H), 3.82-3.80 (m, 8H) 3.76-3.74 (m, 8H), 3.65-3.59 (m, repeating unit), −2.81 (s, 2H)

[0088] MS: MALDI TOP-MS: m/z 1882˜2851 [M+M].sup.+

##STR00012##

Example: Preparation of Antibacterial Polymer Coating Composition and Antibacterial Polymer Film

Example 1

[0089] 100 g of the alkylene oxide (meth)acrylate-based oligomer of Preparation Example 1, 5 g of trimethylolpropane triacrylate (TMPTA), 1 g of the compound of Preparation Example 2 (n=2˜4), 2 g of a photoinitiator (product name: Darocure TPO), 0.1 g of a surfactant (product name: RS90 manufactured by DIC), 50 g of toluene, and 50 g of ethanol were mixed to prepare an antibacterial polymer coating solution (50% solids concentration).

[0090] The antibacterial polymer coating solution (50% solids concentration) was coated using #10 bar, and then cured at a rate of 2 m/min using a UV lamp of 0.2 J/cm.sup.2 to prepare an antibacterial polymer film (10 μm thick).

Example 2

[0091] An antibacterial polymer coating solution (50% solids concentration) and an antibacterial polymer film (10 μm thick) were prepared in the same manner as in Example 1, except that the compound of Preparation Example 2 (n=5˜7) was used instead of the compound of Preparation Example 2 (n=2˜4).

Example 3

[0092] An antibacterial polymer coating solution (50% solids concentration) and an antibacterial polymer film (10 μm thick) were prepared in the same manner as in Example 1, except that the compound of Preparation Example 2 (n=8˜10) was used instead of the compound of Preparation Example 2 (n=2˜4).

COMPARATIVE EXAMPLE

Comparative Example 1

[0093] Ethylene glycol dimethacrylate (EGDMA, Miramer M221, CAS no. 97-90-5) having the following structure was prepared instead of the alkylene oxide (meth)acrylate-based oligomer of Preparation Example 1.

[0094] In addition, TCPP having the following structure was prepared instead of the compound of Preparation Example 2 (n=2˜4).

[0095] An antibacterial polymer coating solution (50% solids concentration) and an antibacterial polymer film (10 μm thick) were prepared in the same manner as in Example 1, except that the ethylene glycol dimethacrylate and TCPP were used.

##STR00013##

Comparative Example 2

[0096] An antibacterial polymer coating solution (50% solids concentration) and an antibacterial polymer film (10 μm thick) were prepared in the same manner as in Comparative Example 1, except that the compound of Preparation Example 2 (n=8˜10) was used instead of the TCPP.

Comparative Example 3

[0097] An antibacterial polymer coating solution (50% solids concentration) and an antibacterial polymer film (10 μm thick) were prepared in the same manner as in Comparative Example 1, except that the alkylene oxide (meth)acrylate-based oligomer of Preparation Example 1 was used instead of the ethylene glycol dimethacrylate.

Experimental Example

Experimental Example 1: Measurement of Antibacterial Activity of Polymer Films of Examples and Comparative Examples

[0098] 1) Preparation of Bacteria Suspension

[0099] E. coli ATCC 8739, the standard E. coli specified in KS L ISO 27447, was used as test bacteria. The E. coli ATCC 8739 strain was inoculated in LB nutrient medium using a platinum loop, cultivated at 37° C. for 16 to 24 hours and then stored in a 5° C. refrigerator. Within one month, a second culture was repeated by replicating the above procedure. The maximum number of CFU (colony forming unit) should be 10 in the second culture. The LB nutrient medium was prepared by mixing 25 g/L Luria Broth powder and 15 g/L agar powder (available from Sigma-Aldrich) in distilled water, sterilizing them in autoclave, and then quantifying them in a petri dish when the temperature dropped to ˜40° C.

[0100] The bacterial culture was centrifuged to separate the bacteria from the LB liquid medium and the bacteria were transferred to saline. The suspension was diluted so that an absorption value of the bacteria-saline solution was 0.5 at 600 nm using a spectrophotometer, and the bacterial suspension was used for the test.

[0101] A specific dilution method may refer to FIG. 2. Each plate was diluted by 1/10, so the number of CFU was reduced by 1/10. An amount of the suspension used for plating was 0.1 ml. The number of CFU of C.sub.4 was 299 and the amount of liquid used was 0.1 ml, so 299 CFU/0.1 ml=2,990 CFU/ml. The number of CFU of C.sub.1 was ˜3.0×10.sup.6 CFU/ml, which is multiplied by 1,000, and C.sub.1 was 1/10 dilution of the bacterial stock solution (C.sub.0), so the number of CFU in the bacterial suspension was 3.0×10.sup.7 CFU/ml.

[0102] 2) Bacteria Inoculation on Test Specimen

[0103] After weighing and placing 0.2 mL of each bacterial suspension (C.sub.1, C.sub.2, C.sub.3, C.sub.4) on the test specimens prepared above, a polypropylene adhesive film having a transmittance of 80% or more was placed thereon to prepare a sandwich structure including a microbial suspension located between the polymer film carrying a photocatalyst sample and the adhesive film.

[0104] 3) Antibacterial Test (Light Condition: Light)

[0105] Each test specimen was placed under a light source and irradiated with light at room temperature (25° C.) for 5 hours. The light used was subjected to conditions of 405 nm and 2 mW/cm.sup.2, and the distance between the test specimen and the light source was 1 cm.

[0106] The results of the experiment are shown in Table 1 and FIG. 3.

TABLE-US-00001 TABLE 1 Addition mole Mole Number of number of EO per 1 EG per 1 mole of Antibacterial mole of oligomer photosensitizer activity (%) Example 1 9 2~4 99.5 Example 2 9 5~7 >99.9 Example 3 9  8~10 >299.9 Comparative 0 0 <90 Example 1 Comparative 0  8~10 90 Example 2 Comparative 9 0 97 Example 3 * Note: The addition mole number of EO means the addition mole number of alkylene oxide repeating units contained per 1 mole of (meth)acrylate-based monomer or oligomer used as a raw material in each of Examples and Comparative Examples.

[0107] In addition, the mole number of EG means the number of moles of ethylene glycol contained per 1 mole of the photosensitizer used as a raw material in each of Examples and Comparative Examples.